CN101503217A - Preparation and use method of dephosphorization carboxyl functionalized nano Fe2O3 adsorbing agent for wastewater - Google Patents

Preparation and use method of dephosphorization carboxyl functionalized nano Fe2O3 adsorbing agent for wastewater Download PDF

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CN101503217A
CN101503217A CNA2009100715200A CN200910071520A CN101503217A CN 101503217 A CN101503217 A CN 101503217A CN A2009100715200 A CNA2009100715200 A CN A2009100715200A CN 200910071520 A CN200910071520 A CN 200910071520A CN 101503217 A CN101503217 A CN 101503217A
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adsorbent
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dtpa
sorbent material
phosphorus
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CN101503217B (en
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任月明
孙伟晓
张密林
马军
魏希柱
江文智
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Rugao Productivity Promotion Center
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Harbin Engineering University
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Abstract

The invention provides a preparation of a wastewater phosphorus removal carboxyl functional nanometer Fe3O4 adsorbent and an application method thereof. The preparation method comprises the following steps: taking FeCl2.4H2O and FeCl3.6H2O as the source of iron grains; dropping sodium hydroxide as a precipitant under the protection of inert gas; preparing a certain dimension of Fe3O4 grains; adding diethylene triaminepentaacetic acid (DTPA) carbonation by utilizing the in-situ composite method during the precipitating and the forming processes of the nanometer Fe3O4 crystal grains; and preparing the black carboxyl functional nanometer Fe3O4 adsorbent, wherein the diameter of the adsorbent is 5 to 20 nm. The preparation and the application of the adsorbent have simple operation steps, low cost and highly-efficient removal effect for phosphate in water; the removal ratio achieves above 99 percent; the adsorbent can be widely applied to the high-concentration phosphoric industrial wastewater and water supply depth phosphorus removal process and can be separated from the solution after being absorbed quickly under an external magnetic field, thereby solving the problem of solid-liquid separation after phosphor is absorbed by the adsorbent; and the adsorbent can be recovered and utilized and has simple and generative method.

Description

Waste water dephosphorization carboxyl functionalized nano Fe 3O 4Preparation of adsorbent and application method
(1) technical field
What the present invention relates to is the sorbent material that a kind of water treatment is used, and the invention still further relates to the application of a kind of water treatment with sorbent material.
(2) background technology
Phosphorus is one of essential element of biological growth, is widely used in industries such as industry, agricultural, medicine, biology simultaneously again.But after the waste water (as surpassing 0.2mg/L) that contains higher concentration phosphorus enters environment water, will constitute harm, and stimulate waterplant hypertrophy such as algae, the contamination phenomenon of eutrophications such as Chi Hu, red tide occur hydrocoles such as fish.Even the waste water after the processing contains the eutrophication that a spot of phosphorus also can cause the lake.There are some researches show that phosphorus is one of element that in the pipe network microbial re-growth is had significant limitation, to most of water quality, when total phosphorus concentration is lower than 1 μ g/L, phosphorus will become the microorganism growth restrictive factor.Therefore phosphorus also can utilize it again in removal and the recovery waste water, and one side can reduce the emission concentration of phosphorus in the waste water, reduces the risk of body eutrophication, can obtain the phosphor resource of preciousness on the other hand.Because phosphor resource is the individual event mobile, along with phosphor resource constantly consumes, phosphorus will become scarce resource.Thereby how to remove the phosphorus of phosphorus, particularly lower concentration in the waste water effectively, and carry out phosphorus and reclaim, be the good method that realizes environmental benefit and economic benefit doulbe-sides' victory, meaning environment, economic, society will be arranged.
At present, sewage dephosphorization technology both domestic and external mainly contains biological process and physico-chemical process.Biological process is to utilize the physiological activity of microorganisms such as polyP bacteria to realize dephosphorization, the synchronous denitrogen dephosphorus technology such as the A that mainly contain traditional activated sludge process, AO method and improved 2O method, PH oredox and BardenpHo method etc., the biological phosphate-eliminating relatively economical has only 30-40% usually but the clearance of phosphorus is low, and single biological process dephosphorization process is difficult to reach the emission standard that is lower than 1mg/L.The materialization rule mainly comprises coagulant sedimentation, ion exchange method, absorption method etc.What the employing of tradition waste water dephosphorization was more is chemical precipitation method, promptly generates the difficultly-soluble phosphates throw out by metal ion and the phosphate radical that adds generations such as one or more molysite, aluminium salt and lime, and separation is removed then.Physical chemistry method can be reduced to phosphorus content the emission standard of 1mg/L.But because molecule quasi-equilibrium phenomenon, cause apparent solubility to amass being much higher than really is solubility product, and in order to reach the formation condition of calcium phosphate precipitation, the precipitation by metallic ion agent concentration that need add is greater than a normal solubility product 1-2 order of magnitude, so medicament expense is with higher.In addition, also exist the sludge quantity that produces big, the moisture percentage in sewage sludge height, the dehydration difficulty is difficult to handle, and is easy to generate shortcomings such as secondary pollution.Simultaneously, the basicity in the raw wastewater causes the part metals precipitation of hydroxide, has also reduced the purity of product, so chemical precipitation method generally only limits to the phosphorus of high-density phosphorus solution is reclaimed.
Absorption method is considered to a kind of effective ways of removing the lower concentration pollutant effluents and handling to advanced water treatment always, and absorption method is having its unique advantage aspect the absorption removal of phosphorus and recovery.The key of this method is how to develop a kind of sorbent material of adsorbable efficiently recovery phosphorus.
(3) summary of the invention
The object of the present invention is to provide a kind of to phosphatic high adsorption capacity, can efficient recovery phosphatic a kind of waste water dephosphorization carboxyl functionalized nano Fe in the waste water 3O 4Sorbent material.
The object of the present invention is achieved like this:
Carboxyl functionalized nano Fe of the present invention 3O 4The preparation of adsorbent method is:
(2) DTPA (diethylene triaminepentaacetic acid(DTPA)) of 2.0～4.5g is mixed with the solution of 0.05～0.1mol/L, adds NaOH to DTPA in the process for preparation and all dissolve;
(2) with the divalent iron salt (FeCl of 3.0～6.0g 24H 2O) and trivalent iron salt (FeCl 36H 2O) ratio that is respectively 2:1 in the mol ratio with DTPA is dissolved in the above-mentioned DTPA solution, makes Fe 2+/ Fe 3+The ratio of/OH-/DTPA amount satisfies 1:1:6:(0.2～1.0).Vigorous stirring under the nitrogen protection effect, and the NaOH solution that adds 1mol/L to regulate pH be 9～10, behind 40 ℃～80 ℃ constant temperature water bath stirring reaction 0.5h, at 60 ℃ of following constant temperature water bath crystallization 2h;
(3) after reaction finishes, above-mentioned solution is carried out solid-liquid separation with magnetic field, and with ethanol and distilled water wash gained solid three times, 60 ℃ of freeze-day with constant temperature 24h; Be ground to fine-powder then, promptly obtain carboxyl functionalized nano Fe 3O 4The sorbent material magnetic particle.
Carboxyl functionalized nano Fe of the present invention 3O 4The application method of sorbent material is:
The sorbent material that makes according to method of the present invention is used to handle the phosphorus-containing wastewater that the phosphoric acid salt starting point concentration is 10～500mg/L, carboxyl functionalized nano Fe 3O 4The add-on of sorbent material is 0.1～4.0g/L, and the pH that reconciles phosphorus-containing wastewater is 3.0～5.0, and the temperature of control absorption is 20～40 ℃, and the absorption duration of oscillation is 0.1～4.0h.
The invention provides a kind of have magnetic and can high efficiency separation phosphorus-containing wastewater preparation of adsorbent and the application method of waste water dephosphorization.Utilize co-precipitation and in-situ compositing, in the preparation nanometer Fe 3O 4Make it give its function of surface carboxylic group by surface modifying method in the process, thereby obtained the surperficial magnetic function sorbent material that is rich in carboxyl, surperficial carboxyl has improved adsorbent surface ground wetting ability on the one hand, reduced its surface tension, strengthen complex microsphere ground stability, improved the ability of phosphate anion in the microsphere surface combination water; On the other hand, this magnetic function sorbent material can also conveniently under externally-applied magnetic field promptly separate, to reach the efficient purpose of removing phosphate radical in the waste water.
The present invention is with FeCl 24H 2O and FeCl 36H 2O is a main raw material, is precipitation agent with NaOH, through co-precipitation, utilize in-situ compositing, in nanometer Fe 3O 4Add diethylene triaminepentaacetic acid(DTPA) (DTPA) in the process that the crystal grain co-precipitation forms and modify a large amount of carboxyls, prepared carboxyl functionalized nano Fe 3O 4Sorbent material, and use this sorbent material and phosphoric acid salt in the waste water is separated and reclaim.Adsorption mechanism mainly be functional group such as carboxyl with phosphate anion between strong, the intermolecular forces effect of electrostatic attraction, hydrogen combine.
This sorbent material diameter is 5-20nm.Preparation of adsorbent of the present invention and application operating step are simple, with low cost, phosphoric acid salt in the water had removal effect efficiently, clearance is up to more than 99%, can be widely used in high-density phosphorus trade effluent and feedwater deep phosphorous removal technology, and under externally-applied magnetic field, from adsorbed solution, separate rapidly, solve the difficult problem of solid-liquid separation behind the adsorbents adsorb phosphorus, recyclable utilization, renovation process is simple.
Advantage of present method and effect are:
(1) modified Nano sorbent material provided by the invention has magnetic, can effectively separate from adsorbed solution rapidly under adding the action of a magnetic field, realizes the rapid efficient of sorbent material.
(2) the present invention utilizes co-precipitation and in-situ compounding process to prepare magnetic Nano Fe 3O 4Sorbent material, and in nanometer Fe 3O 4Introduce carboxyl function group in the forming process, carboxyl quantity in its structure is increased and the binding ability of phosphate radical strengthens.This sorbent material is used for waste water dephosphorization technology, can improve absorption and recovery ability to phosphate radical.
(3) the nano-magnetic sorbent material of the present invention's preparation is with low cost, and synthetic method and process are simple, and used plant and instrument is common common, and as electric mixer, water-bath, three-necked bottle, shaking table etc., reaction conditions is simple, does not have the restriction of harsh experiment condition.Synthetic nano-magnetic sorbent material has higher physical strength, has avoided the swelling of sorbent material in acidic solution to run off.
(4) embodiment
For example the present invention is done in more detail below and describes:
First kind of embodiment of the present invention is:
(1) diethylene triaminepentaacetic acid(DTPA) (DTPA) solid with 0.01mol is dissolved in the 150ml distilled water, and the NaOH that adds a small amount of 1mol/L makes its whole dissolvings;
(2) take by weighing 3.9762g (0.02mol) FeCl 24H 2O and 5.406g (0.02mol) FeCl 36H 2O is dissolved in the above-mentioned DTPA solution, Fe 2+/ Fe 3+The ratio of/OH-/DTPA amount is 1:1:6:0.5, and mixing solutions is transferred to rapidly in the there-necked flask, vigorous stirring under the nitrogen protection effect, and the NaOH solution adjusting pH that adds 1mol/L in the whipping process is 9～10, the best is 10.Behind 60 ℃ of constant temperature water bath reaction 0.5h, at 60 ℃ of following constant temperature water bath crystallization 2h;
(3) with magnetic field above-mentioned solution is carried out solid-liquid separation, and, place 60 ℃ of freeze-day with constant temperature 24h of baking oven with ethanol and distilled water wash gained solid three times; Be ground to fine-powder then, promptly obtain carboxyl functionalized nano Fe 3O 4Magnetic particle.
This sorbent material can be used in waste water dephosphorization, and concrete steps are: get certain density phosphorus-containing wastewater, add a certain amount of carboxyl functionalized nano Fe then 3O 4Sorbent material with the pH value that NaOH or the HCl solution of 0.1mol/L are regulated initial soln, is controlled certain temperature, after vibration absorption reached balance, externally-applied magnetic field separated magnetic adsorbent, with supernatant liquid filtering, filtrate is adjusted to the discharging of neutral back, finishes the waste water dephosphorization technological process.
The phosphoric acid salt starting point concentration is 10～500mg/L in the described waste water, carboxyl functionalized nano Fe 3O 4The add-on of sorbent material is 0.1～4.0g/L, and the pH that reconciles phosphorus-containing wastewater is 3.0～5.0, and the temperature of control absorption is 20～40 ℃, and the absorption duration of oscillation is 0.1～4.0h.
Described vibration adsorption process adopts shaking table to carry out, and the revolution of shaking table is 150～180rpm.
Externally-applied magnetic field is permanent magnet or electromagnetic field described in sorbent material preparation and the adsorption separation process.
The process parameter optimizing of application process is: pH is 3.5, and temperature is 25 ℃, and adsorption time is 1.5h, and the phosphoric acid salt starting point concentration is 300mg/L when following in the waste water to be measured, and the addition of described magnetic adsorbent is that every cubic metre of phosphorus-containing wastewater adds 3kg.
Another embodiment of the present invention is:
1, carboxyl functionalized nano Fe 3O 4Preparation of adsorbent
3.9335g (0.01mol) DTPA solid is placed 150ml distilled water, drip 0.1MNaOH and make its whole dissolvings; With 3.9762g (0.02mol) FeCl 24H 2O solid and 5.406g (0.02mol) FeCl 36H 2The O solid is dissolved in the above-mentioned DTPA solution, and is transferred to mixing solutions in the there-necked flask rapidly, vigorous stirring under the nitrogen protection effect, and the NaOH solution that adds 1mol/L to regulate pH be 9～10, behind 40 ℃～80 ℃ constant temperature water baths reaction 0.5h, at 60 ℃ of following constant temperature water bath crystallization 2h; With magnet above-mentioned solution is carried out solid-liquid separation, and, place 60 ℃ of freeze-day with constant temperature 24h of baking oven with ethanol and distilled water flushing gained solid each three times; Be cooled to room temperature, be ground to fine-powder then, promptly obtain carboxyl functionalized nano Fe 3O 4Magnetic particle.
2, the application method in waste water dephosphorization
Static phosphorus removing method: a certain amount of magnetic sorbent material is added in the 150mL tool plug Erlenmeyer flask, add then in the solution of the certain phosphorus concentration of 20mL, the pH value of regulating initial soln with the NaOH of a small amount of 0.1mol/L or HCl solution, under 25 ℃, the 150r/min rotating speed vibrates down behind the certain hour, with magnet magnetic adsorbent is separated from suspension then, filter, get supernatant liquor and measure residual phosphorus concentration in the filtrate, the clearance and the saturated adsorption capacity of phosphorus are calculated as follows, this test determination index is total phosphorus (TP), and analytical procedure is a molybdenum-antimony anti-spectrophotometric method
E = C o - C e C o × 100 % q = ( C o - C e ) V W
In the formula: E-clearance, %; The q-saturated adsorption capacity, mg/g; C 0Solute concentration before the-absorption, g/L; C eResidual solute concentration in the solution of-absorption back, g/L; The V-liquor capacity, L; The W-adsorbent mass, g.
3, the renovation process of sorbent material
To put into 0.1MNaOH solution with the sorbent material of magnetic field separation behind the absorption phosphorus, the dilute NaOH solution consumption of every gram magnetic adsorbent is 20mL, and mixed solution adsorbs vibration 1.0h, magnetic field fractionation by adsorption under shaking table, sorbent material after the regeneration cleans 2 times with distilled water, and oven dry is ground the back and reused.
4, the feature of Zhi Bei nano-magnetic sorbent material
The magnetic carboxyl-functional sorbent material mean diameter of the present invention's preparation is approximately about 5-20nm.Specific surface area is greater than 80m 2/ g, the width in hole are 36.8nm, and the volume in hole is 2.3189cc/g.Its specific saturation magnetization (Ms) and remanent magnetism (Mr) can reach 4.2emu/g and 1.6emu/g respectively, than pure Fe 3O 4Reduction by 41.0% and 42.4%, keep superparamagnetism.Under the externally-applied magnetic field effect, has good magnetic settling property.At initial phosphate concn is under the 10mg/L situation, the adsorbents adsorb capacity of the present invention's preparation can reach 5～8mg/g, material after adopting 0.1MNaOH solution to absorption is regenerated, can reach 94% to phosphatic desorption efficiency, reusable 6 times, loading capacity keeps 96% of original loading capacity, and is little to the absorption property influence.

Claims (2)

1, a kind of waste water dephosphorization carboxyl functionalized nano Fe 3O 4The preparation of adsorbent method is characterized in that:
(1) DTPA of 2.0～4.5g is mixed with the solution of 0.05～0.1mol/L, adds NaOH to DTPA in the process for preparation and all dissolve;
(2) with the FeCl of 3.0～6.0g 24H 2O and FeCl 36H 2O is dissolved in the above-mentioned DTPA solution in the ratio that the mol ratio with DTPA is respectively 2:1, makes Fe 2+/ Fe 3+/ OH -The ratio of/DTPA amount satisfies 1:1:6:(0.2-1.0), vigorous stirring under the nitrogen protection effect, and the NaOH solution that adds 1mol/L to regulate pH be 9～10, behind 40 ℃～80 ℃ constant temperature water bath stirring reaction 0.5h, at 60 ℃ of following constant temperature water bath crystallization 2h;
(3) after reaction finishes, above-mentioned solution is carried out solid-liquid separation with magnetic field, and with ethanol and distilled water wash gained solid three times, 60 ℃ of freeze-day with constant temperature 24h; Be ground to fine-powder then, promptly obtain carboxyl functionalized nano Fe 3O 4The sorbent material magnetic particle.
2, a kind of waste water dephosphorization carboxyl functionalized nano Fe 3O 4The application of sorbent material is characterized in that: the sorbent material that makes according to the method for claim 1 is used to handle the phosphorus-containing wastewater that the phosphoric acid salt starting point concentration is 10～500mg/L, carboxyl functionalized nano Fe 3O 4The add-on of sorbent material is 0.1～4.0g/L, and the pH that reconciles phosphorus-containing wastewater is 3.0～5.0, and the temperature of control absorption is 20～40 ℃, and the absorption duration of oscillation is 0.1～4.0h.
CN2009100715200A 2009-03-11 2009-03-11 Preparation and use method of dephosphorization carboxyl functionalized nano Fe2O3 adsorbing agent for wastewater Expired - Fee Related CN101503217B (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
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CN101804320A (en) * 2010-05-04 2010-08-18 中国科学院生态环境研究中心 Nano-level iron adsorbent for efficient dephosphorization
CN102633345A (en) * 2012-04-28 2012-08-15 常州亚环环保科技有限公司 Method for treating high-concentration ammonia nitrogen in coal chemical wastewater
CN102976488A (en) * 2012-11-20 2013-03-20 浙江大学 Method for zero-valent nano-iron-reinforced biological removal of nitrogen and phosphorus
CN103908698A (en) * 2014-04-15 2014-07-09 中国人民解放军第四军医大学 Superparamagnetic iron oxide nano-particle-collagen-chitosan magnetic degradable nerve conduit and preparation method thereof
CN103964538A (en) * 2014-05-23 2014-08-06 南京晓庄学院 Method for removing phosphate in water by adsorption of magnetic Fe3O4@SiO2 composite particles modified by cerium oxide
CN105921134A (en) * 2016-06-29 2016-09-07 陕西科技大学 Preparation method and application of DPTA-chitosan modified magnetic adsorbent
CN106745627A (en) * 2016-12-14 2017-05-31 华南师范大学 A kind of sewage dephosphorization agent of easy recovery and its preparation method and application
CN112520902A (en) * 2020-12-17 2021-03-19 梅征 Method for recycling stainless steel pickling and scrubbing water
CN114130351A (en) * 2021-10-29 2022-03-04 神美科技有限公司 Composite metal type adsorbent for deep phosphorus removal and preparation method thereof
CN115487786A (en) * 2022-09-23 2022-12-20 武汉轻工大学 Preparation method of phosphorus removal agent and wastewater treatment method

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101804320A (en) * 2010-05-04 2010-08-18 中国科学院生态环境研究中心 Nano-level iron adsorbent for efficient dephosphorization
CN102633345A (en) * 2012-04-28 2012-08-15 常州亚环环保科技有限公司 Method for treating high-concentration ammonia nitrogen in coal chemical wastewater
CN102976488A (en) * 2012-11-20 2013-03-20 浙江大学 Method for zero-valent nano-iron-reinforced biological removal of nitrogen and phosphorus
CN103908698A (en) * 2014-04-15 2014-07-09 中国人民解放军第四军医大学 Superparamagnetic iron oxide nano-particle-collagen-chitosan magnetic degradable nerve conduit and preparation method thereof
CN103964538A (en) * 2014-05-23 2014-08-06 南京晓庄学院 Method for removing phosphate in water by adsorption of magnetic Fe3O4@SiO2 composite particles modified by cerium oxide
CN103964538B (en) * 2014-05-23 2015-11-18 南京晓庄学院 A kind of magnetic Fe of cerium oxide modification 3o 4SiO 2granular absorption removes phosphatic method in water body
CN105921134A (en) * 2016-06-29 2016-09-07 陕西科技大学 Preparation method and application of DPTA-chitosan modified magnetic adsorbent
CN106745627A (en) * 2016-12-14 2017-05-31 华南师范大学 A kind of sewage dephosphorization agent of easy recovery and its preparation method and application
CN112520902A (en) * 2020-12-17 2021-03-19 梅征 Method for recycling stainless steel pickling and scrubbing water
CN114130351A (en) * 2021-10-29 2022-03-04 神美科技有限公司 Composite metal type adsorbent for deep phosphorus removal and preparation method thereof
CN115487786A (en) * 2022-09-23 2022-12-20 武汉轻工大学 Preparation method of phosphorus removal agent and wastewater treatment method
CN115487786B (en) * 2022-09-23 2023-08-18 武汉轻工大学 Preparation method of dephosphorizing agent and wastewater treatment method

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